Emulsifiers and toxicants containing the same



EMULSIFIERS AND TOXICANTS CONTAINING THE SAME Herbert L. Sanders, EdwardA. Knaggs, and Marvin L. Nnsshaum, Chicago, Ill.

N Drawing. Application May 3, 1954 Serial No. 427,382

13 Claims. (Cl. 167-42) This invention relates to emulsions for use foragricultural and livestock purposes and is especially concerned withimprovements in emulsifier compositions and emulsifiabletoxicant-containing concentrates which utilize said emulsifiercompositions.

In the past several years, various toxicants for use for :withemulsifying agents and organic solvents to form concentrates which, inuse, are added to water to form emul- 'sions which are sprayed orotherwise applied to the surface of the plants, weeds, animals orinsects to be treated.

Numerous types of emulsifying agents have been suggested and employedfor the above purposes, typical of .such agents being mono-glyceridesand diglycerides of rosin acids and higher molecular weight-fatty acids;polyoxyalkylene ethers of alkyl phenols .as, forexample,-polyoxyethylene ethers of di-isobutyl phenol;. partial estersof rosin acids and higher molecular weight fatty acids with hexitolanhydrides such as sorbitan mono-oleate, sorbitan :trioleate, andthelike; sodium 'alkylnaphthalene sulfo- :nates, sodiumtetrahydronaphthalene sulfonate, sodium salts of aryl alkyl polyethersulfonates,-sodium salts-of alkylated aromatic sulfonates, and the like;polyoxyethylene derivatives of hexitol anhydrides partially esterifiedwith rosin acids and higher molecular weight fatty acids,

'such as polyoxyethylene sorbitan mono-oleate, polyoxyethylene sorbitanmonostearate, and the like. Such emulsifying agents are, generallyspeaking, reasonably effective in various formulations and underparticular conditions. However, they tend to lack certainversatility'and have a number of other objections with which thoseversed in the art are familiar.

In accordance with the present invention, substantially improvedemulsifiers or emulsifying compositions have been evolved, beingparticularly effective when utilized in conjunction with toxicants suchas toxaphene,DDT, and the like. Such toxicant concentrates form goodemulsions by simple addition to water, requiring little or .no

agitation, and stable emulsions are obtained not only with soft-waterbut, at least as well, in most cases, with hard .water and also watercontaining substantial amounts-of electrolytes, for example, sea water.

The emulsifying compositions utilized in accordance with the presentinvention comprise mixtures of at least two ingredients, hereafterdescribed in detail. Supplemental ingredients may, if desired, be addedbut they are not essential so far as the present invention is concerned.

cal containing from 8 to 18 carbon atoms.

H, p I

Patented Feb. 3,

The first of the two essential ingredients comprises a non-ionicemulsifier of the type which is a derivative of a polyglycol,particularly a polyoxyethylene glycol or polyoxypropylene glycol,especially the former, the number of oxyalkylene groups present ranging,generally speaking, from about an average of 4 to as high as 60 or more.In the preferred embodiments of the invention, the polyglycol portion ofthe molecule should contain from about 8 to about 20 oxyalkylene groups,especially, as stated above, oxyethylene groups. From a molecular weightstandpoint, the polyoxyethylene glycol radical of the non-ionicemulsifying agents advantageously ranges from a molecular weight betweenabout 200 and about 6000, with molecular weights of about 300 to about1000 being preferred in most cases. Some of them are conventionallyprepared by reacting, for example, a higher molecular weight acid suchas lauric acid or oleic acid, or a higher molecular weight alcohol suchas lauryl or oleyl alcohol, or a higher molecular weight aliphatic orfatty mercaptan such as lauryl mercaptan, or a higher molecular Weightaliphatic amine such as lauryl amine or oleyl amine or stearyl amine, ora higher molecular weight aliphatic carboxylic amide such as lauramideor the lauric acid amide of monoethanolamine, with ethylene oxide tointroduce the desired number of oxyethylene groups. Others are made byreacting a phenol or a naphthol or an alkylated isocyclic hydroxylcompound such as an alkylated phenol or naphthal, particularly where thealkyl group contains from about 4 and especially from 8 to 18carbonatoms, with ethylene oxide to introduce the requisite number ofoxyethylene groups.

Such products are available on the marketunder a variety of trademarksand their method of preparation is well known. It is particularlydesirable to utilize those which are Watersoluble or water-dispersible.Typical examples which are useful as one of the constituents of theemulsifying compositions made in accordance with the present inventionare as follows:

Tweens which are fatty acid mono-esters of anhydro sorbitols whichhavebeen solubilized by etherification of the free hydroxyl groups withethylene oxide.- The fatty acid portion of the molecule is commonlyderived from lauric acid, palmitic acid, oleic acid, and stearic acid,or mixtures thereof. The number of oxyethylene groups varies withinappreciable limits. Typical of such Tweens are those sold under the nameTween 20, which is a polyethylene glycol derivative of sorbitanrnono-laurate; Tween 60, which is a polyethylene glycol derivative ofsorbitan mono-stearate; and Tween which is a polyethylene glycolderivative of sorbitan mono-oleate.

A number of the products sold under the name Tritons are likewiseeffective for use in the practice of the present invention, in themanner described hereafter. The Tritons are higher molecular weightalkyl phenol polyglycol ethers, in certain cases, dimeric alkyl phenolpolyglycol ethers, the higher molecular weight alkyl radi- Typicalexamples comprise reaction products of p-tert-octyl phenol with ethyleneoxide wherein a number of oxyethylene radicals are introduced into themolecule. Among this type of nonionic emulsifiers are products soldunder the name of Triton X-I OO and Triton X-155.

Various others of nonionic agents usefulin the practice of the presentinvention are, for example, those sold under a variety of other tradenames as, for example, Igepal, Antarox A-400, Emulphor, Peregal, NekalRU, Nonics, Ethomeens and Ethomids.

Others of the nonionic agents which fall within the scope of thoseusable in accordance with the present invention, are as indicated above,those sold under the trademarks Merj, which is a higher fatty acid esterof a poly- '3 ethylene glycol, and Brij, which is a Iauryl ether of apolyethylene glycol.

In general, in the nonionic agents used herein, the polyglycol radicalis'ether-linked or ester-linked to a higher molecular weight radicalwhich contains at least 8 and, most advantageously, from 12 to 22 carbonatoms. Such higher molecular weight radical can, for example, be acarboxylic acid acyl radical derived from any one, or mixtures of anytwo or more, of the following acids: caprylic, capric, lauric, myristic,palmitic, oleic, ricinoleic, stearic, linoleic, linolenic, said acidsand others being derived or derivable from animal or vegetable sources,for example, lard, coconut oil, rapeseed oil, sesame oil, palm kerneloil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow,soya bean oil, peanut oil, tall oil, castor oil, seal oils, whale oil,shark oil; waxes such as beeswax and spermaceti; partially or completelyhydrogenated animal and vegetable oils such as those mentioned;carboxylic acids derived, by oxidation and other methods, frompetroleum; oxidized and/ or polymerized higher fatty acids or higherfatty acids derived from oxidized and/or polymerized triglyceride oils;abietic acid and rosin and resinic acids; hydroxy and alpha-hydroxyhigher aliphatic and fatty acids such as i-hydroxy stearic acid,dihydroxystearic acid, .alpha-hydroxy stearic acid, alpha-hydroxypalmitic acid, alpha-hydroxy lauric acid, alpha-hydroxy coconut oilmixed fatty acids, and the like. In general, the acids can be straightchain or branched chain and saturated or unsaturated.

In the case of the higher molecular weight ether and thioetherderivatives of the polyglycols the higher molecular weight radical canbe derived from alcohols and mercaptans corresponding to theabove-mentioned acids as, for example, lauryl alcohol, lauryl mercaptan,oleyl alcohol, oleyl mercaptan, etc. Other sources of the highermolecular weight radicals are acylated and alkylated phenols andnaphthols as, for example, diisobutyl phenol, isooctyl phenol, dodecylphenol, p-tert-octyl phenol, octyl naphthols,undecyl-para-oxyphenylketone, tridecyl-paraoxyphenylketone, etc., saidlatter radicals corresponding to the formulae:

(1) Alk-*Ar-O (2) Ac-Ar-O-- where Alk is an alkyl radical containingfrom 4 and particularly from 8 to 18 carbon atoms, Ac is an acyl radicalcontaining from 4 and particularly from 8 to 18 carbon atoms, and Ar isa benzene or naphthalene radical.

Typical specific examples of the first of said ingredients are:

Oleic acid mono-ester of polyoxyethylene glycol (300) Mixture of monoanddi-esters (oleic) of polyoxyethylene glycol (400) Abietic acidmono-ester of polyoxyethylene glycol (600) Mixed soya bean oil fattyacid monoand diesters of polyoxyethylene glycol (400) Polyoxyethyleneglycol ether of di-isobutyl phenol (300) Oleic acid mono-ester ofpolyoxyethylene glycol (1000) Polyoxyethylene glycol *ether ofpara-isooctylphenol (500) Polyoxyethylene glycol ether ofisododecylphenol (400) Polyoxyethylene glycol ether of dodecylnaphthol(600) Polyoxyethylene glycol ether of undecyl-paraoxyphenylketone (400)Polyoxyethylene glycol ether of iso-amyl phenol (40()) Tall oil fattyacid monoand di-esters of polyoxyethylene glycol (600) Rosin fatty acidmono-esters of polyoxyethylene v glycol (400) Oleyl mono-ether ofpolyoxyethylene glycol (400) Polyoxyethylene glycol ether of mono-nonylphenol (2000) {Average molecular weight of polyoxyethylene glycol fromWhlCll the esters and ethers are prepared.

The second of said two essential ingredients comprises an oil solublealkaline earth metal salt of an alkylated naphthalene sulfonic acid, thealkyl radical containing from 8 to 18 carbon atoms. Especiallysatisfactory are the calcium salts of mono-alkylated naphthalenemonosulfonic acids wherein the alkyl radical contains predominately from12 to 16 carbon atoms. At least most of said compounds can berepresented by the general formula where Alk is an alkyl radical, n isan integer from 1 to 3 with the proviso that (Alk),, contains from 8 to18 carbon atoms, Ar is a naphthalene radical, and M is an alkaline earthmetal.

Others of said second group of ingredients can be represented by thegeneral formula where Alk is an alkyl radical, n is an integer from 1 to3 with the proviso that (Alk),, contains from 8 to 18 carbon atoms, M isan alkaline earth metal, and R is a member selectedfrom the groupconsisting of hydrogen, methyl, phenyl, hydroxy-phenyl, particularlymono-hydroxyphenyl, and hydroxyl. Although, in the above formula, the R,Alk and $0 M groups are shown as being present in only one of the fusedbenzene rings, theformula given is intended to encompass said compoundswhether said R, Alk and $0 M groups are present in the same or differentfused benzene rings.

Typical examples of compounds falling into the category of the second ofsaid essential ingredients are the calcium, strontium, magnesium andbarium salts'of the following: di-butyl naphthalene monosulfonic acid;monolauryl naphthol monosulfonic acid; dioctyl naphthalene monosulfonicacid; mono-nonyl naphthalene monosulfonic acid; mono-myristylnaphthalene monosulfonic acid; mono-cetyl naphthyl monosulfonic acid;di-nonyl naphthalene monosulfonic acid; isododecyl naphthalenemono-sulfonic acid; mono-stearyl naphthalene monosulfonic acid;mono-stearylnaphthalene monosulfonic acid; triisopropyl naphthalenemonosulfonic acid; monostearyl, mono-lauryl.naphthalene disulfonic acid;monolauryl naphthol monosulfonic acid; and the like.

The higher molecular weight alkyl radical present in the alkylatednaphthalene sulfonates can be derived from olefins, polymerized olefins,chlorinated hydrocarbons, and the like in accordance with knownpractices. As a general rule, the alkyl radicals will comprise mixtureshaving varying chain lengths and they can be selected or fractionsprepared so that the desired chain length in predominate amount ispresent.

It will be understood that mixtures of any two or more of theingredients of the first group may be utilized in conjunction withmixtures of any two or more of the ingredients of the second group.

Supplemental agents having solvent and coupling characteristics may beused and desirably are utilized but are not essential so far as theimportant features of the invention are concerned. Typical examples ofsuch solvents and coupling agents are Z-methyl pentanediol-LZ; methylnaphthalene; xylene; and dipropylene and tripro pylene glycol methylethers.

It should be noted that the alkali metal salts, for example, the sodiumsalts, of the alkylated naphthalene sulfonates, although heretoforeknown and used as emulsifying agents, are relatively ineffective whenused either per se or in conjunction with the non-ionic p'olyglycolemulsifiers for the purposes of my present invention. It may also benoted that the alkaline earth metal salts of the alkylated naphthalenesulfonates are likewise per se ineffective but, when used, inconjunction with the nonionic polyglycol emulsifiers described above,they surprisingly act very radically to synergize the functioning of thelatter emulsifiers and make possible the unusually efiective resultswhich are achieved through the practice of the present invention. Theseunusual results involve imparting an extremely high degree offiash-dispersibility or self-dispersibility in aqueous media to thetoxicant concentrates. When the alkaline earth sulfonates are utilizedas the sole emulsifier in the toxicant concentrates, or when thenon-ionic polyglycol emulsifiers are utilized as the sole emulsifiers(except under certain conditions, at relatively high concentrations) inadmixture with the toxicant concentrates, the latter, when added towater, normally fall through the water as oily droplets and do not tendto disperse until the system is agitated. However, when the mixture ofthe alkaline earth sulfonates and the nonionic emulsifiers is used evenin relatively low concentrations in admixture with the toxicantconcentrates, the latter, when added to water, disperse readily or flashdisperse into a cloud substantially as soon as they strike the water andhighly eltective dispersions are obtained without any necessity :foragitation. This result is of particular importance in conjunction withthe use of spray equipment where little or no agitation is provided orfeasible as, for example, in aeroplane spray tanks, knacksackspray'tanks, and in many pieces of farm equipment, cattle dipping vats,and the like. As indicated above, although the alkaline earth sulfonatesand the nonionic polyglycol emulsifiers are comparatively pooremulsifiers and dispersers for toxi cant concentrates, a tremendous andwholly unexpected self-dispersing eifect is obtained when the two areutilized in conjunction with each other.

The proportions of the ingredients can be varied within appreciablelimits. Thus, for example, the first ingredient can be present ingreater or lesser proportions than the second ingredient. In most cases,a ratio of 1 to 9, and particularly 3 to 7, parts of the firstingredient to 9 to 1, and particularly 7 to 3, parts of the secondingredient, said parts being by weight, is satisfactory. When used'tomake toxicant concentrates, the emulsifier mixture will'usua-llyrangefrom about 5% to;about by weight although the proportions may rangesomewhat below or somewhat abovethat range, as hereafter more fullypointed out. In any event, it will be understood that the optimumproportions will vary, depending upon the particular toxicant ortoxicant mixture utilized, upon the selection of the particularemulsifier mixture employed, and upon the particular alkaline earthmetal salt selected.

The following examples are illustrativeof emulsifiers made-in accordancewith the invention. It will be appreciated that numerous othercompositions can be made, in the light of the teachings herein, bymodifications of proportions, selections of other combinations of ingrerclients, and the. like, all within the scope of the invention as set outin. the appended claims. In the exa iples, the numeral appearing inparentheses represents the molecular weight of the polyoxyethyleneglycol. All parts listed by weight.

Example 1 Parts Mono-hexadecyl naphthalene monosulfonic acid,

Triton X-155 7 Example 4 Parts Mono-stearyl naphthalene monosulfonicacid, Ca

salt 3.5 Ethofat 242/25 1.5

Example 5 Mono-lauryl naphthalene monosulfonic acid, Mg

salt 3.5 Ethofat 242/25 1.5

Example 6 Mono-lauryl naphthalene monosulfonic acid, Ca

salt 2.5 Antarox A-400 2.5

Example 7 Mono-myristylnaphthalene monosulfonic acid, Ba

salt 1.25 Ethofat 242/25 3.75

Example 8 Mono-myristyl naphthalene monosulfonic acid, Ca

salt 3 Oleic acid mono-ester of polyoxyethylene glycol Example 9Mono-lauryl naphthol monosulfonic acid, Ca salt 6 Tall oil mixed monoanddi-esters of polyoxyethylene glycol (400) 4 Example 10 Mono-cetylnaphthol monosulfonic acid, Mg salt 7 Tall oil mixed monoanddi-esters ofpolyoxyethylene glycol (500) 3 Example 11 Mono-lauryl naphthalenemonosulfonic acid, Ca

salt 3 Oleyl mono-ether of polyoxyethylene glycol (400).. 1

Example 12 Mono-lauryl naphthalene mono-sulfonic acid, Ca

salt 7 Polyoxyethylene glycol ether of para-isooctyl phenol Toxicantcompositions or concentrates, adapted readily to produce an emulsionupon the addition of water, are formed by the incorporation with theemulsifier compositions of the desired toxicant, whether thelatter be aninsecticide, hebicide, plant hormone, fungicide, or the like. Suchtoxicant compositions advantageously contain one or more toxicants, theemulsifier proper, and an organic solvent or mixture of solvents, withor without various supplemental agents, so that all that it is necessaryfor the ultimate user to do is to disperse the composition in therequisite amount of water and spray or otherwise apply it to the surfaceto be treated. The proportions of toxicant used in such toxicantcompositions are variable within wide limits although, in the usualcase, the toxicant in the concentrate will range from about 20% to about50%. The amount of organic solvent will, in general, range from about30% to 60%, and the emulsifier composition will usually be present inproportions of about 5% to about 10%. The organic solvent or mixturesmay be selected from a large group, typical examples of which arekerosene, Z-methyl pentanediol-LZ, benzene, toluene, polymethylnaphthalenes, pine oil, and the like.- The dilution with Water to formthe emulsions .7 V for spraying or the like may likewise vary withinwide limits so that, for example, ultimate emulsions may be madecontaining from a fraction of one percent to several percent, forinstance, of the toxicant or mixture of toxicants.

Illustrative or typical examples of toxicant compositions falling withinthe scope of the invention are as follows, all parts listed being byweight:

Example 14 Parts Toxaphene 65 Kerosene 25 Emulsifier of Example 1 Whilevarious mixing procedures may be employed, it is preferred to dissolvethe toxicant (in this case toxaphene) in the solvent (in this casekerosene) and stir until the mixture is clear. The emulsifier is thenadded and" stirred until clear. In use, the desired or requisite amountof toxicant concentrate is poured into'the predetermined amount of waterand the resulting emulsion is then ready for application to the surfacesto be treated by spraying or in any other desired manner.

The compositions of the following examples are made up in like manner toExample 14 and made into emulsions with water in similar fashion.

Example 15 v Parts DDT Xylene 75 Emulsifier of Example 2 5 Example 16Chlordane 60 Kerosene 30 Emulsifier of Example 1 10 Example 17 Toxaphene50 Kerosene 40 Emulsifier of Example 4 10 Example 18 Toxaphene 35 DDT 35Xylene 70 Emulsifierof Example 6 10 Example 19 Toxaphene 57 Kerosene 33Emulsifier of Example 3 1O Example 20 DDT Velsicol AR 50 (polymethylnaphthalene aromatic solvent) 70 Emulsifier of Example 4 5 Example 21DDT 25 Velsicol AR 50 70 Emulsifier of Example 7 5 Example 22 lien genehexachloride 25 Xylene 65 Emulsifier of Example 6 l0 Example 23Toxaphene a--. 64 Kerosene 26 Emulsifier of Example 13 10 :The pH -ofthe emulsifier, when dispersed in water,

should ordinarily range from about 5 to about 8, particularly desirableresults being obtained in most cases at a pH of about 6. The pH isadjusted to the desired value, in the manufacture of the alkylatednaphthalene sulfonate during the neutralization step, by controlling theamount of alkaline earth metal oxide or hydroxide added to the alkylatednaphthalene sulfonic acid.

The emulsifiers, as described above, have especial utility for thepreparation of emulsions for agricultural and livestock purposes, but itwill be understood that their utility extends to other fields whereemulsions of oleaginous and aqueous materials are desired.

While the invention has been described in detail, no unnecessarylimitations should by reason thereof be inferred, and it should beunderstood that the scope of the invention is not to be limited therebybut is pointed out in the appended claims.

This application is a continuation-in-part of application Serial No.290,334, filed May 27, 1952, now Patent No. 2,696,453.

What is claimed as new and desired to be protected by Letters Patent ofthe United States is:

1. An agricultural and livestock composition for use in conjunction withorganic solvent solutions of waterinsoluble toxicants, which, upon theaddition thereof to soft as well as hard waters, forms a fine dispersiontherein of said toxicants, said composition containing (a) at least onenonionic emulsifier selected from the group consisting of highermolecular weight ethers and thioethers of polyoxyethylene glycols andhigher molecular weight carboxylic acid esters of polyoxyethyleneglycols, the higher molecular weight radicals containing from 8 to 22carbon atoms and the polyoxyethylene glycol radical having a molecularweight between about 200 and 6000, and (b) an oil-soluble compoundcorresponding to the formula where Alk is an alkyl radical, n is aninteger from 1 to 3, (Alk),, containing from 8 to 18 carbon atoms, Ar isa member selected from the group consisting of the naphthalene radicaland its methyl and hydroxyl monosubstituents, and M is an alkaline earthmetal selected from the group consisting of calcium and magnesium, saidingredient (a) and said ingredient (b) being pres ent in proportions toeach other ranging from about 9 to 1 to about 1 to 9.

2. A composition in accordance with claim 1, wherein said ingredient (b)is a calcium salt of an alkyl naphthalene monosulfonate, the alkylradical containing from 8 to 18 carbon atoms.

3. An agricultural and livestock composition for use in conjunction withorganic solvent solutions of waterinsoluble toxicants, which, upon theaddition thereof to soft as well as hard waters, forms a fine dispersiontherein of said toxicants, said composition containing (a) at least onenonionic emulsifier selected from the group consisting of water-solubleto water-dispersible higher molecular weight alkyl ethers and thioethersof polyoxyethylene glycols and higher molecular weight aliphaticcarboxylic acid esters of polyoxyethylene glycols, the higher molecularweight alkyl and aliphatic carboxylic acid radicals containing from 12to 22 carbon atoms and the polyoxyethylene glycol radical having amolecular weight between about 200 and 6000, and (b) an oil-solublealkaline earth metal salt of an alkyl naphthalene sulfonate wherein thealkyl radical contains from 12 to 16 carbon atoms and wherein thealkaline earth metal is selected from the group consisting of calciumand magnesium, said ingredient (a) and said ingredient (b) being presentin proportions to each other ranging from about 9 to l to about 1 to 9.

4. An agricultural and livestock composition for use in conjunction withorganic solvent solutions of waterinsoluble toxicants, which, upon theaddition thereof to soft as well as. hard waters,forms a fine dispersiontherein of said toxicants, said composition containing (a) a nonionicemulsifier inthe form of a higher molecular weight fatty acid ester of apolyoxyethylene glycol, the higher molecular weight fatty acid radicalcontaining from 12 to 22 carbon atoms and the polyoxyethylene glycolradical having a molecular weight between about 200 and 6000, and (b) anoil-soluble compound corresponding to the formula where Alk is an alkylradical, n is an integer from 1 to 3, (Alk),, containing from 8 to 18carbon atoms, M is an alkaline earth metal selected from the groupconsisting of calcium and magnesium, and R is a member selected from thegroup consisting of hydrogen, methyl and hydroxyl, said ingredient (a)and said ingredient (b) being present in proportions to each otherranging from about 9 to l to about 1 to 9.

5. An agricultural and livestock composition for use in conjunction withorganic solvent solutions of waterinsoluble toxicants, which, upon theaddition thereof to soft as well as hard waters, forms a fine dispersiontherein of said toxicants, said composition containing (a) a nonionicemulsifier in the form of a higher molecular weight fatty acid ester ofpolyoxyethylene glycol ether of a sugar alcohol of the class consistingof mannitan and sorbitan, the higher molecular weight fatty acid radicalcontaining from 12 to 22 carbon atoms and the polyoxyethylene glycolradical having a molecular weight between about 200 and 6000, and (b) anoil-soluble compound corresponding to the formula isa Where Alk is analkyl radical, n is an integer from 1 to 3, (Alk) containing from 8 to18 carbon atoms, M is an alkalineearth metal selected from the groupconsisting of calcium and magnesium, and R is a member selected from thegroup consisting of hydrogen, methyl and hydroxyl, said ingredient (a)and said ingredient (b) being present in proportions to each otherranging from about 9 to l to about 1 to 9 6. An'agricultural andlivestock composition for use in conjunction with organic solventsolutions of waterinsoluble toxicants, which, upon the addition thereofto soft as well as hard waters, forms a fine dispersion therein of saidtoxicants, said composition containing (a) a nonionic emulsifier in theform of an alkyl phenol polyoxyethylene glycol ether, the alkyl radicalcontaining from 8 to 18 carbon atoms and the polyoxyethylene glycolradical having a molecular weight between about 300 and 600, and (b) anoil-soluble compound corresponding to the formula where Alk is an alkylradical containing from 8 to 18 carbon atoms, M is an alkaline earthmetal selected from the group consisting of calcium and magnesium, and Ris a member selected from the group consisting of hydrogen, methyl andhydroxyl, said ingredient (a) and said ingredient (b) being present inproportions to each other ranging from about 9 to 1 to about 1 to 9.

7. Ari agricultural and livestock composition for use in conjunctionwith organic solvent solutions of waterinsoluble toxicants, which, uponthe addition thereof to soft as well as hard waters, forms a finedispersion therein of said toxicants, said composition containing (a) anon-ionic emulsifier emulsifier in the form of a normally liquidwater-soluble to water-dispersible compound having a polyoxyethyleneglycol radical containing from 4 to 60 ethenoxy groups linked to ahigher molecular weight radical containing from 8 to 22 carbon atoms,and (b) an oil-soluble compound corresponding to the formula Alk whereAll: is an alkyl radical containing from 8 to 18 carbon atoms, and M isan alkaline earth metal selected from the group consisting of calciumand magnesium, and R is a member selected from the group consisting ofhydrogemmethyl and hydroxyl, said ingredient (a) and said ingredient (b)being present in pro-portions to each other ranging from about 9 to l toabout 1 to 9.

8. An agricultural and livestock composition for use in conjunction withorganic solvent solutions of waterinsoluble toxicants, which, upon theaddition thereof to soft as well as hard waters, forms a fine dispersiontherein of said toxicants, said composition containing (a) a non-ionicemulsifier in the form of a watersoluble to water-dispersible compoundincluding a polyoxyethylene glycol radical containing from 4 to 60oxyethylene groups linked to a higher molecular weight radicalcontaining from 8 to 22 carbon atoms, and (b) an oil-soluble compoundcorresponding to the formula where Alk is an alkyl radical, n is aninteger from 1 to 3, (Alk) containing from 8 to 18 carbon atoms, Ar is amember selected from the group consisting of the naphthalene radical andits methyl and hydroxyl monosubstituents, and M is an alkaline earthmetal selected from the group consisting of calcium and magnesium, saidingredient (a) and said ingredient (b) being present in proportions toeach other ranging from about 9 to 1 to about 1 to 9. v

9. An agricultural and livestock composition for use in conjunction withorganic solvent solutions of waterinsoluble toxicants, which, upon theaddition thereof to soft as well as hard waters, forms a fine dispersiontherein of said toXicants, said composition containing (a) a non-ionicemulsifier in the form of a water-soluble to water-dispersible compoundhaving a polyoxyethylene radical containing from about 8 to about 20oxyethylene groups linked to a higher molecular weight radicalcontaining from 8 to 22 carbon atoms, and (b) an oil-sol-, uble calciumsalt of an alkylated napthalene sulfonate in which the alkyl radicalcontains from 8 to 18 carbon atoms, said ingredient (a) and saidingredient (b) being present in proportions to each other ranging fromabout 9 to l to about 1 to 9.

10. A toxicant concentrate composition, adapted readily, upon theaddition to soft as well as hard waters, to form a fine dispersion ofthe toxicant in said water, said composition containing, in parts byweight of the composition as a whole, from about 20% to about 50% of atleast one organic solvent-soluble water-insoluble toxicant, from about30% to about 60% of organic solvent for said toxicant, and from about 5%to about 10% of a mixture of (a) a non-ionic emulsifier in the form of anormally liquid water-soluble to water-dispersible compound having apolyoxyethylene glycol radical containing from 4 to 60 ethenoxy groupslinked to a higher molecular weight radical containing from 11 8 to 22carbon atoms, and (b) an oil-soluble compound corresponding to theformula Alk where Alk is an alkyl radical containing from 8 to 18 carbonatoms, and M is an alkaline earth metal selected from the groupconsisting of calcium and magnesium, and R is a member selected from thegroup consisting of hydrogen, methyl and hydroxyl, said ingredient (a)and said ingredient (b) being present in proportions to each otherranging from about 9 to 1 to about 1 to 9. V

11. A toxicant concentrate composition, adapted readily, upon theaddition to soft as Well as hard waters, to form a fine dispersion ofthe toxicant in said water, said composition containing, in parts byweight of the composition as a whole, from about 20% to about 50% of atleast one organic solvent-soluble water-insoluble toxicant, from about30% to about 60% of organic solvent for said toxicant, and from about toabout 10% of a mixture of (a) a non-ionic emulsifier in the form of awater-soluble to water-dispersible compound having a polyoxyethyleneradical containing from about 8 to about oxyethylene groups linked to ahigher molecular weight radical containing from 8 to 22 carbon atoms,and (b) and oil-soluble calcium salt of an alkylated naphthalenesulfonate in which the alkyl radical contains from 8 to 18 carbon atoms,said ingredient (a) and said ingredient (b) being present in proportionsto each other ranging from about 9 to 1 to about 1 to 9.

12. A toxicant concentrate composition, adapted readily, upon theaddition to soft as well as hard waters, to form a fine dispersion ofthe toxicant in said Water, said composition containing, in parts byweight of the composition as a whole, from about 20% to about 50% of atleast one organic solvent-soluble water-insoluble toxicant,

from about 30% to about 60% of organic solvent for said toxicant, andfrom about 5% to about 10% of a mixture of (a) water-soluble towater-dispersible non-ionic emulsifier in the form of, alkyl phenolpolyoxyethylene glycol ether, the alkyl radical containing from 8 to 18carbon atoms and the polyoxyethylene glycol radical having a molecularweight between about 300 and 600, and (b) calcium salt of mono-dodecylnaphthalene mono-sulfonic acid, said ingredient (a) and said ingredient(b) being present in proportions to each other of about 3 to 1 to about1 to 3.

13. A toxicant concentrate composition, adapted readily, upon theaddition to soft as well as hard waters, to form a fine dispersion ofthe toxicant in said water, said composition containing, in parts byweight of the compo sition as a whole, from about 20% to about of atleast one organic solvent-soluble water-insoluble toxicant, from about30% to about of organic solvent for said toxicant, and from about 5% toabout 10% of a mixture of (a) water-soluble to water-disperisble nonionic emulsifier in the form of a higher molecular Weight fatty acidmono-ester of polyoxyethylene glycol ether of sorbitan, the highermolecular weight fatty acid radical containing from 12 to 18 carbonatoms and the polyoxyethylene glycol radical having a molecular weightbetween about 300 and 600, and (b) calcium salt of mono-dodecylnaphthalene mono-sulfonic acid, said ingredient (a) and said ingredient(b) being present in proportions to each other'of about 3 to 1 to about1 to 3.

' References Cited in the file of this patent UNITED STATES PATENTSSchrauth Mar. 11, 1930 Sanders et al Dec. 7, 1954 OTHER REFERENCES

1. AN AGRICULTURAL AND LIVESTOCK COMPOSITION FOR USE IN CONJUNCTION WITHORGANIC SOLVENT SOLUTIONS OF WATERINSOLUBLE TOXICANTS, WHICH, UPON THEADDITION THEREOF TO SOFT AS WELL AS HARD WATERS, FORM A FINE DISPERSIONTHEREIN OF SAID TOXICANTS, SAID COMPOSITION CONTAINING (A) AT LEAST ONENONIONIC EMULSIFER SELECTEED FROM THE GROUP CONSISTING OF HIGHERMOLECULAR WEIGHT ETHERS AND THIOETHERS OF POLYOXYETHYLENE GLYCOLS ANDHIGHER MOLECULAR WEIGTHT CARBOXYLIC ACID ESTERS OF POLYOXYETHYLENEGLYCOLS, THE HIGHER MOLECULAR WEIGHT RADICALS CONTAINING FROM 8 TO 22CARBON ATOMS AND THE POLYOXYETHYLENE GLYCOL RADICAL HAVING A MOLECULARWEIGHT BETWEEN ABOUT 200 AND 6000, AND (B) AND OIL-SOLUBLE COMPOUNDCORRESPONDING TO THE FORMULA